Covalent organic frameworks (COFs) are thermodynamically stable, crystalline, highly porous polymer networks with potential applications in chemical separation, catalysis, and energy devices. The COF crystalline structure is predictable, dictated by simple molecular building blocks, and properties such as pore diameter are modulated through choice of precursor monomer. While this approach is, ideally, highly modular, the optimal COF synthesis conditions vary from system to system; these conditions are often determined empirically and without insight into the overall guiding principles. Here we present a systematic characterization of the synthesis of a variety of boronate ester and boroxine COFs. The frameworks are synthesized from fully homogeneous conditions, and the rates of formation characterized primarily from optical turbidity measurements. By comparing the relative sensitivities to reaction conditions, we identify the key properties controlling COF formation and develop a general model for rational COF synthesis and the development of new materials.

Mechanistic understanding and guiding principles of covalent organic framework formation

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.